CN108619919A - The novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count for Liquid-liquid separation is 6 - Google Patents

The novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count for Liquid-liquid separation is 6 Download PDF

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CN108619919A
CN108619919A CN201810431156.3A CN201810431156A CN108619919A CN 108619919 A CN108619919 A CN 108619919A CN 201810431156 A CN201810431156 A CN 201810431156A CN 108619919 A CN108619919 A CN 108619919A
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hole
liquid
branched
trunk
filter membrane
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张永斌
袁虹娣
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/021Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/024Oxides
    • B01D71/027Silicium oxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/02Details relating to pores or porosity of the membranes
    • B01D2325/021Pore shapes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a kind of novel tree-shaped nanoscale cylindrical hole filter membranes that branch's hole count for liquid-liquid separation is 6, there are many an equally distributed tree cylindrical holes for manufacture in one layer of solid material, each through-hole is including a larger trunk hole and six compared with subbranch hole, this six branched holes are parallel with their trunk hole and are connected to completely with this trunk hole, and trunk hole surface material is identical with its branched hole surfacing;Each branched hole is filter opening, its length determines according to filter opening intensity requirement, and trunk hole is for reducing filter membrane flow resistance, and physical absorption is weak between a kind of liquid and trunk hole surface in liquid mixture to be separated, physical absorption is strong between remaining liquid and trunk hole surface, and each branch's pore radius is:RB, 1=(0.1~0.2) Rcr, RcrTo make that liquid in the liquid mixture that physical absorption is weak between trunk hole surface become critical cylindrical hole radius needed for continuous media flowing, this layer of solid material is filter membrane.

Description

The novel tree-shaped nanoscale cylindrical hole that branch's hole count for Liquid-liquid separation is 6 Filter membrane
Technical field
The present invention relates to filter membrane field, specifically a kind of branch's hole count for Liquid-liquid separation be 6 it is novel Tree-shaped nanoscale cylindrical hole filter membrane.
Background technology
Filtering film, abbreviation filter membrane have important application in industry and daily life, it can be used for filtering out solid Grain, impurity purify liquid, it can also be used to filter out bacterium, macromolecular substances, or the separation for realizing two kinds of liquid.It is daily In life, filter membrane can be used for purifying drinking water, purify various beverages, it can also be used to impurity, the various ions in seawater are filtered out, it is real Existing seawater cleaning.Existing typical filter ways and means have:
One, activated carbon filters
Activated carbon is a kind of industrial adsorbents that purposes is extremely wide, it be using charcoal, various shells and fat coal etc. as Raw material, raw material is crushed by physics and chemical method, is sieved, activation of catalyst, rinsing, drying and screening etc. it is a series of Process fabricates.The adsorptivity of activated carbon is derived from its unique molecular configuration, and there are many holes in the inside of activated carbon, often If the internal void drawout of gram activated carbon can reach 500~1700 square metres, exactly this unique internal structure makes Obtaining activated carbon has excellent adsorption capacity.When activated carbon filters, due to the fine content in the adsorbable various liquid of its porosity Matter, decoloration, deodorization, dechlorination, organics removal and the heavy metal being usually used in water process remove synthetic detergent, bacterium, virus And the polluters such as radioactivity, it is also commonly used for the tertiary treatment of waste water.
The common application range of activated carbon filtering:(1) water treatment facilities filtering, sewage disposal, Treated sewage reusing etc. are used for. It is widely used in chemical industry, food, medicine, electronics photovoltaic etc..(2) it is used to require delivery turbidity≤5mg/L that can meet drinking water quality Industrial water, domestic water and the municipal water supply system of standard.(3) removal of the suspended matter, solids in trade effluent.(4) It can be used as the pre-processing device in ion-exchange softening, desalting system, the coarse filtration of the industrial water supply not high to water quality requirement Equipment.(5) swimming pool circulating treating system, cooling cycle water purification system etc. are used in.The advantage and disadvantage of activated carbon filtering:Advantage: Activated carbon price is relatively inexpensive, and it is relatively low that activated carbon filters cost, can meet general industry and the common filtration needs of daily life, resistance to Pressure, heat-resisting, sexual valence is relatively high.Disadvantage:The hole of activated carbon is larger, it is difficult to realize fine filtering, cannot filter out micron order and receive The substance of meter level size, is usually used in coarse filtration.
Two, micro-pore-film filtration
It is close and numerous on microporous barrier to be evenly distributed with each micropore, the diameter in this hole usually 0.1 micron and 100 microns it Between.Therefore, microporous barrier can filter out liquid, gas 0.1um or more particle and bacterium, it has, and filtering accuracy is high, transition speed Degree is fast, absorption falls off less, without medium, acid-alkali-corrosive-resisting, it is easy to operate the advantages that.Be widely used in medicine, chemical industry, electronics, The required equipment of the industry such as beverage, fruit wine, biochemical water process, environmental protection.
Common microporous membrane filter element has:Polytetrafluoroethylene film (PTFE) filter core gathers inclined film (PVDF) filter core, polypropylene screen (PP) filter core, cellulose acetate film (CN-CA) filter core, nylon (PN6) filter core, alloy stud, Wire-wound filter core, melt-blown filter, PA/PE Sintered filter core.These filter core features are:It is small, light-weight, easy to use, filter area is big, plugging rate is low, the rate of filtration Soon, pollution-free, the dilute stability of heat and chemical stability are good, can filter out most particles, be widely used in refined filtration and degerming work Skill.
The shortcomings that micro-pore-film filtration:Compared to nano-pore filter membrane, the diameter in filtering hole is still bigger than normal on microporous barrier, although energy Meet many refined filtration requirements in daily industry and life, but cannot be used for filtering superfine small substance such as blood purification, protein Middle virus purification, liquid intermediate ion filter out, the super purification etc. of water.
Three, sock filtration
Micron order liquid filter bag is made using high-quality filtrate, can effectively remove the solid for needing to remove in liquid Matter.When by micron order filter bag, impurities are accurately captured in filter bag deep layer liquid, complete filter process.Filter material Matter:Different according to institute's filtering solution, PE felts or PP felts may be selected in filter material, and the filtrates such as nylon monofilament, polyester monofilament also can be selected, from And it is widely used in height different temperatures, soda acid varying environment.
Similar with micro-pore-film filtration, the shortcomings that sock filtration, is:The diameter in filtering hole is still bigger than normal on filter bag, although can be full Many refined filtration requirements in the daily industry of foot and life, but cannot be used for filtering in superfine small substance such as blood purification, protein Virus purification, liquid intermediate ion filter out, the super purification etc. of water.
Four, nano-pore membrane filtration
In order to filter pole subtitle substance, isolated viral, separation larger molecular organics etc., nano-pore filter membrane mistake must be just used Filter.Compared to miillpore filter, the hole in nano-pore filter membrane is much smaller, and diameter is in nanometer scale, often less than by filter impurity Molecular dimension, therefore be usually used in hyperfine filtering, impurity, bacterium, virus, organic macromolecule etc. can thoroughly be filtered out.Nanometer Kong Changwei cylindrical holes, conical bore in the filter membrane of hole.To improve this filter membrane permeability, also have using two layers of filter membrane, upper layer is to receive Metre hole filter membrane, lower layer are miillpore filter.Also someone develops very thin monolayer nano-pore graphene filter membrane, this filter membrane Permeability is preferable.
Although the filter capacity of nano-pore filter membrane is strong, since filter opening is minimum, this permeability of the membrane is poor, its filtering Efficiency is relatively low, and this film is very thin, and the mechanical strength of film also often faces the challenge, not high pressure resistant, high temperature.Filter capacity is oozed Permeability and mechanical strength are difficult to realize well simultaneously on nano-pore filter membrane;One of which performance is met, must be reduced Remaining performance.
Five, Liquid-liquid separating and filtering
It often needs the liquid for being blended in two kinds one piece to separate in daily life and production, realizes Liquid-liquid separation Filtering.In the past, the common means of Liquid-liquid isolation of purified had:
(1) Gravity Separation:The two kind liquid larger and immiscible suitable for density difference.It is larger in two kinds of fluid density differences In the case of, the larger liquid of density can be deposited on bottom, and the smaller liquid of density can float on upper layer, can be achieved with two kinds in this way The separation of liquid.
(2) centrifugal force separate:The two kind liquid larger and immiscible suitable for density difference.It is generated using rotary drum high speed rotation Powerful centrifugal force field, keep density different and two kinds of immiscible liquid mixtures achieve the purpose that separation.
(3) it extracts:Suitable for the little two kinds of miscible liquid of solubility.With another solvent from the mixture of both liquid Extract solute.Precondition is:Two kinds of solvents are immiscible, and solubility of the solute in two kinds of solvents differs greatly.
(4) it distills:Two kinds of liquid of larger suitable for boiling point difference and mutual phased soln.Make that lower liquid of boiling point by heating Evacuator body realizes the separation of both liquid.
Liquid-liquid separating and filtering is a more difficult technical barrier in filtering.The common Liquid-liquid of above-mentioned introduction Separation means are limited to two kinds of specific physical property and differ larger liquid, for example density difference is big and mutually insoluble or boiling point phase Solubility of the poor big or solute in two kinds of solvents differs greatly.The two kinds of liquid to mix in daily life or production are often Do not have these conditions, these liquid of isolation of purified just face larger technical barrier.It mixes for example, density difference is little and mutually Solution, two kinds of liquid mix similar in boiling point, and how detaching both liquid, to be conventional means presented hereinbefore cannot solve 's.
Invention content
The object of the present invention is to provide a kind of novel tree-shaped nanoscales that branch's hole count for Liquid-liquid separation is 6 Cylindrical hole filter membrane, solves to be only limited to two kinds of specific physical property of separation in the prior art to differ larger liquid and be difficult to partition density It is not much different and mutually phased soln, two kinds of this technical barriers of liquid similar in boiling point.
Technical solution of the invention is:
The novel tree-shaped nanoscale cylindrical hole filter membrane that a kind of branch's hole count for Liquid-liquid separation is 6, such as Fig. 1 and Shown in Fig. 2, in the inner manufacture of one layer of solid material (1), there are many through-hole of equally distributed tree, each trees Through-hole include a trunk hole (2) and six branched hole, that is, branched holes (3), branched hole (4), branched hole (5), branched hole (6), Branched hole (7) and branched hole (8), this six branched holes are mutually parallel with trunk hole (2) and connect completely with trunk hole (2) Logical, trunk hole (2) and this six branched holes are cylindrical hole, the surface of the surfacing and this six branched holes of trunk hole (2) Material all same, each branched hole are filter opening, and each branch's pore radius is RB, 1, each branch's hole length is l1, trunk hole (2) With the surface coatings of its six branched holes or be not coated by coating, several liquid to be separated mix made of mixing The physical absorption between a kind of liquid and trunk hole (2) and the surface of its branched hole in object is weak, remaining in liquid mixture Physical absorption between liquid and trunk hole (2) and the surface of its branched hole is strong, strong between liquid here and trunk hole (2) surface Physical absorption instigates liquid flowing in trunk hole (2) to become critical trunk hole (2) diameter of continuous media flowing not less than 30nm Liquid and trunk hole (2) surface between physical absorption, between liquid here and trunk hole (2) surface weak physical absorption instigate master Liquid flowing becomes liquid of critical trunk hole (2) diameter of continuous media flowing no more than 10nm and trunk hole in dry hole (2) (2) physical absorption between surface;Branched hole (3) diameter is in nanometer scale, branched hole (3) radius RB, 1It is taken as (0.1~0.2) Rcr, R herecrIt is situated between to make that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) become continuous Mass flow moves required critical cylindrical hole radius.Each branch's hole length l1It is as small as possible to reduce the flow resistance of filter opening, l1Value root Determine that the axial line of each branched hole and the parallelism tolerance of the axial line in their trunk hole (2) are little according to filter opening intensity requirement In 0.1l1.The radius R in trunk hole (2)B, 2Than its branch pore radius RB, 1Bigger, trunk hole (2) radius RB, 2According to its point Branch pore radius RB, 1And that liquid between trunk hole (2) surface in the weak liquid mixture of physical absorption in filter membrane most Big penetrating power requires to be calculate by the following formula determination:
Here, λ0=l1/ l, l are the thickness of solid material (1),Req=c1RB, 1, RcrTo make and master That liquid between the surface of dry hole (2) in the weak liquid mixture of physical absorption becomes the critical circle needed for continuous media flowing Post holes radius, c1Value range be:1.40~1.72, c1Preferred value be 1.56,ρ is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure Liquid mixture in that liquid body phase density,Physical absorption is weak between the surface of trunk hole (2) That liquid in liquid mixture is R in radiuseqHole radial direction averag density, this averag density withHave It closes,η is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure Liquid mixture in that liquid bulk viscosity,Physical absorption is weak between the surface of trunk hole (2) That liquid in liquid mixture is R in radiuseqHole radial direction equivalent viscosity, this equivalent viscosity withHave It closes,It is in radius to describe that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) ReqHole radial direction present Discontinuous transmission effect parameter.
Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branched hole (8) are uniformly distributed On a circumference on the surface of solid material (1), the radius of the circumference is Rd, this branched hole (3), branched hole (4), branch The distribution circle and trunk hole (2) of hole (5), branched hole (6), branched hole (7) and branched hole (8) on the surface of solid material (1) Concentricity tolerance is not more than 0.1Rd, spacing of the contiguous branch hole on the circumference is Δ1, Δ1With RB, 1Ratio value range For:ks1/RB, 1=0.05~0.5, RdWith RB, 1Ratio be:Rd/RB, 1=(6+3ks)/π。
The thickness l of solid material (1) is determined according to the requirement of mechanical strength of solid material (1);Trunk hole (2) and its six The through-hole for the tree that a branched hole is formed runs through solid material (1), trunk hole (2) in the thickness direction of solid material (1) It is inner in solid material (1) for reducing that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) Flow resistance, increase solid material (1) penetrating power.Under the conditions of in this way, due to a kind of liquid in liquid mixture Physical absorption between trunk hole (2) and its branch's hole surface it is weak and in liquid mixture remaining liquid and trunk hole (2) and Physical absorption between its branch's hole surface is strong, and the liquid in liquid mixture is in the inner flow resistance of solid material (1) with regard to phase Difference is very big, that liquid between trunk hole (2) and its branch's hole surface in the weak liquid mixture of physical absorption can be suitable Profit is by solid material (1), and remaining liquid in liquid mixture is then difficult to through solid material (1).This solid material (1) The novel tree-shaped nanoscale cylindrical hole filter membrane that as the signified branch's hole count for Liquid-liquid separation of the present invention is 6.
Further, filter membrane uses plane or curved surface filter membrane.
Further, the thickness of filter membrane is identical everywhere or differs.
Further, filter membrane is fabricated by silica or graphene.
The novel tree-shaped nanoscale cylindrical hole filter membrane that this kind is 6 for branch's hole count of Liquid-liquid separation, it is solid with one layer Body material manufacture filter membrane, filter membrane can be plane filter membranes, can also be curved surface filter membrane.Filter membrane thickness can be equal everywhere, also may be used To be variation.
The beneficial effects of the invention are as follows:
Compared to traditional liquid-liquid separation technology, present invention does not require each fluid density differences in liquid mixture Big or boiling point differs greatly, and does not also require each liquid in liquid mixture immiscible, has specific tree by design The filter membrane of through-hole makes flow resistance of the liquid in liquid mixture in filter membrane differ greatly, to realize Liquid-liquid point From;Filter membrane of the present invention can not only realize the separating and filtering of Liquid-liquid, moreover it is possible to meet requirement of mechanical strength when filtering;This hair Bright filter membrane anufacturability is good, of low cost, to the good separating effect of Liquid-liquid.These are advantages of the present invention.The present invention There is important application in the fields such as sewage disposal, oil-oil separation, biology, pharmacy, petrochemical industry, chemical industry.
Description of the drawings
Fig. 1 is the novel tree-shaped nanoscale cylindrical hole that the embodiment of the present invention is 6 for branch's hole count of Liquid-liquid separation The front view of filter membrane structure;Fig. 2 is that the novel tree-shaped that the embodiment of the present invention is 6 for branch's hole count of Liquid-liquid separation is received The left view of meter level cylindrical hole filter membrane structure;
Fig. 3 is the water in embodiment when filter membrane of the present invention is manufactured with silica, detached to water and machine oil mixture With dimensionless flow resistance I of the machine oil in filter membrane of the present inventionfWith filter opening, that is, branched hole (3) radius RB, 1Relational graph;
Fig. 4 be when filter membrane of the present invention is manufactured with graphene, is detached to water and machine oil mixture in embodiment water and Dimensionless flow resistance I of the machine oil in filter membrane of the present inventionfWith filter opening, that is, branched hole (3) radius RB, 1Relational graph.
In Fig. 1 and Fig. 2:1- solid materials, 2- trunks hole, 3- branched holes, 4- branched holes, 5- branched holes, 6- branched holes, 7- Branched hole, 8- branched holes
Wherein, l1For each branch's hole length, l2For the length of main dry hole (2), l is thickness, that is, embodiment of solid material (1) The thickness of filter membrane of the present invention, RdFor branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branch Hole (8) is in the radius of the distribution circle on the surface of solid material (1), Δ1Point for contiguous branch hole on the surface of solid material (1) Spacing on the circumference of cloth circle.
Specific implementation mode
The preferred embodiment that the invention will now be described in detail with reference to the accompanying drawings.
Embodiment
The novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count for Liquid-liquid separation of embodiment is 6, such as schemes Shown in 1 and Fig. 2, in the inner manufacture of one layer of solid material (1), there are many through-hole of equally distributed tree, each tree-shaped knots The through-hole of structure includes a trunk hole (2) and six branched hole, that is, branched holes (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branched hole (8), this six branched holes are mutually parallel with trunk hole (2) and complete with trunk hole (2) Connection, trunk hole (2) and this six branched holes are cylindrical hole, the table of the surfacing and this six branched holes of trunk hole (2) Plane materiel material all same, each branched hole are filter opening, and each branch's pore radius is RB, 1, each branch's hole length is l1, trunk hole (2) and the surface coatings of its six branched holes or it is not coated by coating, made of several liquid to be separated mix The physical absorption between a kind of liquid and trunk hole (2) and the surface of its branched hole in mixture is weak, in liquid mixture Physical absorption between remaining liquid and trunk hole (2) and the surface of its branched hole is strong, liquid here and trunk hole (2) surface Between strong physical absorption critical trunk hole (2) diameter of instigating liquid flowing in trunk hole (2) to become continuous media flowing be not less than Weak physical absorption refers between physical absorption between the liquid and trunk hole (2) surface of 30nm, liquid here and trunk hole (2) surface Liquid flowing in trunk hole (2) is set to become liquid of critical trunk hole (2) diameter no more than 10nm and master that continuous media flows Physical absorption between dry hole (2) surface;Branched hole (3) diameter is in nanometer scale, branched hole (3) radius RB, 1Be taken as (0.1~ 0.2)Rcr, R herecrConnect to make that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) become Critical cylindrical hole radius needed for continuous media flow.Each branch's hole length l1It is as small as possible to reduce the flow resistance of filter opening, l1's Value is according to the determination of filter opening intensity requirement, the parallelism tolerance of the axial line of each branched hole and the axial line in their trunk hole (2) No more than 0.1l1.The radius R in trunk hole (2)B, 2Than its branch pore radius RB, 1Bigger, trunk hole (2) radius RB, 2According to it Branch pore radius RB, 1And that liquid between trunk hole (2) surface in the weak liquid mixture of physical absorption is in filter membrane Maximum penetrating power require be calculate by the following formula determination:
Here, λ0=l1/ l, l are the thickness of solid material (1),Req=c1RB, 1, RcrTo make and master That liquid between the surface of dry hole (2) in the weak liquid mixture of physical absorption becomes the critical circle needed for continuous media flowing Post holes radius, c1Value range be:1.40~1.72, c1Preferred value be 1.56,ρ is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure Liquid mixture in that liquid body phase density,Physical absorption is weak between the surface of trunk hole (2) That liquid in liquid mixture is R in radiuseqHole radial direction averag density, this averag density withHave It closes,η is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure Liquid mixture in that liquid bulk viscosity,Physical absorption is weak between the surface of trunk hole (2) That liquid in liquid mixture is R in radiuseqHole radial direction equivalent viscosity, this equivalent viscosity withHave It closes,It is in radius to describe that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) ReqHole radial direction present Discontinuous transmission effect parameter.
Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branched hole (8) are uniformly distributed On a circumference on the surface of solid material (1), the radius of the circumference is Rd, this branched hole (3), branched hole (4), branch The distribution circle and trunk hole (2) of hole (5), branched hole (6), branched hole (7) and branched hole (8) on the surface of solid material (1) Concentricity tolerance is not more than 0.1Rd, spacing of the contiguous branch hole on the circumference is Δ1, Δ1With RB, 1Ratio value range For:ks1/RB, 1=0.05~0.5, RdWith RB, 1Ratio be:Rd/RB, 1=(6+3ks)/π。
The thickness l of solid material (1) is determined according to the requirement of mechanical strength of solid material (1);Trunk hole (2) and its six The through-hole for the tree that a branched hole is formed runs through solid material (1), trunk hole (2) in the thickness direction of solid material (1) It is inner in solid material (1) for reducing that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) Flow resistance, increase solid material (1) penetrating power.Under the conditions of in this way, due to a kind of liquid in liquid mixture Physical absorption between trunk hole (2) and its branch's hole surface it is weak and in liquid mixture remaining liquid and trunk hole (2) and Physical absorption between its branch's hole surface is strong, and the liquid in liquid mixture is in the inner flow resistance of solid material (1) with regard to phase Difference is very big, that liquid between trunk hole (2) and its branch's hole surface in the weak liquid mixture of physical absorption can be suitable Profit is by solid material (1), and remaining liquid in liquid mixture is then difficult to through solid material (1).This solid material (1) The novel tree-shaped nanoscale cylindrical hole filter membrane that as the signified branch's hole count for Liquid-liquid separation of the present invention is 6.
In one preferred embodiment, filter membrane is plane filter membrane, and filter membrane is fabricated by graphene, for detaching water and machine oil Mixture (the hydrophobic close machine oil of graphene).Select branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) With branched hole (8) radius, that is, filter opening radius RB, 1=0.7nm, takes ks1/RB, 1=0.5, c1=1.56, λ0=l1/ l=1 × 10-2, the thickness of whole film, that is, solid material (1) is l=1 μm, then:Each branch's hole length l1=10nm, trunk hole (2) radius RB, 2=3.9nm, distribution radius of circle R of each branched hole on the surface of solid material (1)d=1.7nm, contiguous branch hole is in this point Separation delta on cloth circumference1=0.35nm;Take the depth of parallelism of the axial line of each branched hole and the axial line in their trunk hole (2) Tolerance is 1.0nm, takes each branched hole to be in the distribution circle on the surface of solid material (1) and the concentricity tolerance of trunk hole (2) 0.16nm.Water flow resistance in this filter membrane is smaller, can pass through filter membrane;And flow resistance is very in this filter membrane for machine oil Greatly, filter membrane cannot be passed through.It can be achieved with the separation of water and machine oil in this way.
In one preferred embodiment, filter membrane is plane filter membrane, and filter membrane is fabricated by silica, for detaching water and machine Oil mixture (silicon dioxide drainage parent machine oil).Select branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branched hole (8) radius, that is, filter opening radius RB, 1=0.7nm, takes ks1/RB, 1=0.5, c1=1.56, λ0=l1/ l=1 ×10-4, the thickness of whole film, that is, solid material (1) is l=0.1mm, then:Each branch's hole length l1=10nm, trunk hole (2) Radius RB, 2=11nm, distribution radius of circle R of each branched hole on the surface of solid material (1)d=1.7nm, contiguous branch hole is at this Separation delta on circumferential spread1=0.35nm;Take the axial line of each branched hole parallel with the axial line in their trunk hole (2) Degree tolerance is 1.0nm, takes each branched hole to be in the distribution circle on the surface of solid material (1) and the concentricity tolerance of trunk hole (2) 0.16nm.Water flow resistance in this filter membrane is smaller, can pass through filter membrane;And flow resistance is very in this filter membrane for machine oil Greatly, filter membrane cannot be passed through.It can be achieved with the separation of water and machine oil in this way.
In one preferred embodiment, filter membrane is plane filter membrane, and filter membrane is fabricated by graphene, for detaching water and alcohol Mixture (the hydrophobic close alcohol of graphene).Select branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) With branched hole (8) radius, that is, filter opening radius RB, 1=0.5nm, takes ks1/RB, 1=0.5, c1=1.56, λ0=l1/ l=1 × 10-2, the thickness of whole film, that is, solid material (1) is l=1 μm, then:Each branch's hole length l1=10nm, trunk hole (2) radius RB, 2=2.2nm, distribution radius of circle R of each branched hole on the surface of solid material (1)d=1.2nm, contiguous branch hole is in this point Separation delta on cloth circumference1=0.25nm;Take the depth of parallelism of the axial line of each branched hole and the axial line in their trunk hole (2) Tolerance is 1.0nm, takes each branched hole to be in the distribution circle on the surface of solid material (1) and the concentricity tolerance of trunk hole (2) 0.11nm.Water flow resistance in this filter membrane is smaller, can pass through filter membrane;And flow resistance is very in this filter membrane for alcohol Greatly, filter membrane cannot be passed through.It can be achieved with the separation of water and alcohol in this way.
In one preferred embodiment, filter membrane is plane filter membrane, and filter membrane is fabricated by silica, for detaching water and vapour Oil mixture (silicon dioxide drainage parent gasoline).Select branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branched hole (8) radius, that is, filter opening radius RB, 1=0.6nm, takes ks1/RB, 1=0.5, c1=1.56, λ0=l1/ l=1 ×10-4, the thickness of whole film, that is, solid material (1) is l=0.1mm, then:Each branch's hole length l1=10nm, trunk hole (2) Radius RB, 2=8.7nm, distribution radius of circle R of each branched hole on the surface of solid material (1)d=1.4nm, contiguous branch hole exist Separation delta on the circumferential spread1=0.3nm;Take the flat of the axial line of each branched hole and the axial line in their trunk hole (2) Row degree tolerance is 1.0nm, takes each branched hole in the concentricity tolerance of the distribution circle and trunk hole (2) on the surface of solid material (1) For 0.13nm.Water flow resistance in this filter membrane is smaller, can pass through filter membrane;And gasoline flow resistance in this filter membrane It is very big, filter membrane cannot be passed through.It can be achieved with the separation of water and gasoline in this way.
Principle of this kind for the novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count of Liquid-liquid separation is 6 is said It is bright as follows:
Filter membrane of the present invention is used for Liquid-liquid separating and filtering, and a kind of liquid in liquid mixture is allowed to pass through filter membrane, And remaining liquid in liquid mixture is allowed to be difficult to through filter membrane, to reach Liquid-liquid separation.The principle of the invention is to utilize The larger physical absorption of difference of each liquid in the small nano-size pores (filter opening) of filter membrane between orifice surface in liquid mixture Characteristic is so that each liquid has the prodigious flow resistance of difference in filter membrane in liquid mixture.To realize Liquid-liquid Purpose is detached, the present invention claims:A kind of liquid and filter membrane in mixture made of several liquid to be separated mix Physical absorption between small nano-size pores (filter opening) surface is weak, and the small nano-size pores of remaining liquid and filter membrane in liquid mixture Physical absorption between surface is strong.Here strong physical absorption instigates liquid flowing in filter opening to become continuous between liquid and filter opening surface Physical absorption between liquid and filter opening surface of the critical filter opening diameter of media flow not less than 30nm, liquid here and filter opening Weak physical absorption instigates liquid flowing in filter opening to become the critical filter opening diameter of continuous media flowing no more than 10nm's between surface Physical absorption between liquid and filter opening surface.
The filter opening radius of filter membrane of the present invention, that is, branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and the radius R of branched hole (8)B, 1Value range be (0.1~0.2) Rcr, R herecrTo make the physics between filter opening surface inhale That liquid in attached weak liquid mixture becomes the critical cylindrical hole radius needed for continuous media flowing.Filter opening of the present invention is straight Diameter 2RB, 1It is horizontal to be generally in 1nm magnitudes.Different liquids in liquid mixture to be separated in the filter membrane designed so just With the flow resistance to differ greatly to realize the Liquid-liquid separation function of filter membrane.
The requirement of mechanical strength proposed to filter membrane during Liquid-liquid separating and filtering is considered, with conventional material such as dioxy The thickness l of filter membrane of the present invention made of SiClx need to usually reach 50 μm or more.If penetrating filter of the present invention using single filter opening The whole thickness l of film, then filter opening seem very deep, the draw ratio of filter opening greatly (reaches 104).Liquid is it is difficult to flow through this and thin And long filter opening, the penetrating power of such filter membrane just becomes very poor.In fact, the axial direction of filter opening, that is, each branched hole is long in the present invention Spend l1(i.e. the depth of filter opening) need not reach the thickness l of filter membrane, only need to consider filter opening intensity requirement, it is long to reserve necessary filter opening Spend l1.In this way, can achieve the purpose that Liquid-liquid separating and filtering.On the other hand, in order to reduce and filter opening i.e. branched hole (3) resistance of that liquid flow filter membrane between surface in the weak liquid mixture of physical absorption, increases the penetrating power of filter membrane, The trunk hole (2) that fluid flow in six filter openings of dense distribution i.e. six branched holes can be pooled to a bigger is inner, quilt The liquid of separating and filtering flows out filter membrane by trunk hole (2), and material is thus formed the through-holes of tree in filter membrane.
According to nanochannel fluid flow theory, six branched hole, that is, branched holes (3) shown in Fig. 2, branched hole (4), point It is l that branch hole (5), branched hole (6), branched hole (7) and branched hole (8), which are equivalent to a length,1Radius with hole is ReqIt is straight Cylindrical hole.The radius R in trunk hole (2)B, 2It is bad if too small, it cannot reach and effectively lower the resistance of liquid flow filter membrane and have Effect increases the purpose of filter membrane penetrating power.And the radius R of trunk hole (2)B, 2It is excessive, it is also bad;The radius of trunk hole although (2) RB, 2Increase can reduce the resistance of single tree through-hole in liquid flow filter membrane, still, for a given filter membrane, Its surface area is given, the radius R of trunk hole (2)B, 2Increase the sum of trunk hole (2) in filter membrane can be made to reduce, in this way The penetrating power of filter membrane is set to be deteriorated instead, the flow for flowing liquid through filter membrane reduces.Therefore, trunk hole how is chosen in the present invention (2) radius RB, 2It is crucial.
The radius R in trunk hole (2)B, 2It need to make that in the liquid mixture that physical absorption is weak between trunk hole (2) surface Liquid has maximum penetrating power in filter membrane, and according to this requirement, based on fluid flow theory in nanochannel, the present invention obtains To the radius R of trunk hole (2)B, 2With all branched holes of trunk hole (2) it is equivalent at cylindrical hole radius ReqIt need to meet with ShiShimonoseki It is formula:
Here, λ0=l1/ l, l are that the thickness of solid material (1) is the thickness of filter membrane of the present invention,Req =c1RB, 1, RcrIt is situated between to make that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) become continuous Mass flow moves required critical cylindrical hole radius, c1Value range be:1.40~1.72, c1Preferred value be 1.56,ρ is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure Liquid mixture in that liquid body phase density,Physical absorption is weak between the surface of trunk hole (2) That liquid in liquid mixture is R in radiuseqHole radial direction averag density, this averag density withHave It closes,η is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure Liquid mixture in that liquid bulk viscosity,Physical absorption is weak between the surface of trunk hole (2) That liquid in liquid mixture is R in radiuseqHole radial direction equivalent viscosity, this equivalent viscosity withHave It closes,It is in radius to describe that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) ReqHole radial direction present Discontinuous transmission effect parameter.
By the radius R of the counted trunk hole (2) of above formulaB, 2Than its branch pore radius RB, 1It is much greater, in remaining filter Film thickness (l-l1) on open up trunk hole (2), allow liquid by trunk hole (2) flow out filter membrane can be substantially reduced filter membrane flowing hinder Power, the penetrating power for significantly increasing filter membrane.For ensure trunk hole (2) six branched holes dense distribution and meet these branches The manufacturing process in hole requires, here the circumferential distance Δ in contiguous branch hole1It should meet:ks1/RB, 1=0.05~0.5, this six Distribution radius of circle R of a branched hole in filter membrane surfacedIt should meet:Rd/RB, 1=(6+3ks)/π.In this way, the filter membrane that the present invention designs Just have the advantages that more tree number of through-holes, good penetrability, high mechanical strength, anufacturability are good.Here it is the present invention Principle.
When filter membrane of the present invention is manufactured with silica, is detached to water and machine oil mixture, reality is set forth in Fig. 3 Apply the dimensionless flow resistance I of water and machine oil in filter membrane of the present invention in examplefWith filter opening, that is, branched hole (3) radius RB, 1Relationship. In Fig. 3,Here, Rr=10nm, ρ and η are respectively the body of water or machine oil under environment temperature and pressure Phase density and bulk viscosity, l are the thickness of filter membrane of the present invention in embodiment, AmFilter opening is distributed with for filter membrane of the present invention in embodiment Surface area, χ be embodiment in filter membrane of the present invention be distributed with trunk hole (2) surface drilling rate, ifFor in embodiment The dimension flow resistance of filter membrane of the present invention, if=Δ p/qm, qmFor flowed through in the unit time in embodiment the water of filter membrane of the present invention or The mass flow of machine oil, Δ p are the pressure difference applied on filter membrane of the present invention in embodiment.As can be seen from Figure 3, work as RB, 1≤2nm When, flow resistance of the machine oil in filter membrane of the present invention is more than 65~1000 times of flow resistance of the water in filter membrane of the present invention;This Show that flow resistance difference of both liquid in filter membrane of the present invention is very big.Fig. 3 shows that water can be suitable in filter membrane of the present invention Profit passes through, and machine oil is then difficult to filter membrane through the invention.Fig. 3 supports the present invention.
When filter membrane of the present invention is manufactured with graphene, is detached to water and machine oil mixture, implementation is set forth in Fig. 4 The dimensionless flow resistance I of water and machine oil in filter membrane of the present invention in examplefWith filter opening, that is, branched hole (3) radius RB, 1Relationship.Figure In 4, IfDefinition it is identical as in Fig. 3, as can be seen from Figure 4, work as RB, 1When≤2nm, flow resistance of the machine oil in filter membrane of the present invention It is more than 65~1000 times of flow resistance of the water in filter membrane of the present invention;Which show both liquid in filter membrane of the present invention Flow resistance difference is very big.Fig. 4 shows that water can pass through in filter membrane of the present invention, and machine oil is then difficult to filter through the invention Film.Fig. 4 supports the present invention.

Claims (8)

1. the novel tree-shaped nanoscale cylindrical hole filter membrane that a kind of branch's hole count for Liquid-liquid separation is 6, feature exist In:In the inner manufacture of one layer of solid material (1), there are many through-hole of equally distributed tree, the through-holes of each tree Including a trunk hole (2) and six branched hole, that is, branched holes (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) it is mutually parallel and is connected to completely with trunk hole (2), trunk with trunk hole (2) with branched hole (8), this six branched holes Hole (2) and this six branched holes are cylindrical hole, and the surfacing of trunk hole (2) and the surfacing of this six branched holes are homogeneous Together, each branched hole is filter opening, and each branch's pore radius is RB, 1, each branch's hole length is l1, trunk hole (2) and its six The surface coatings of a branched hole are not coated by coating, and one in mixture made of several liquid to be separated mix Physical absorption between kind liquid and trunk hole (2) and the surface of its branched hole is weak, remaining liquid in liquid mixture and master Physical absorption between dry hole (2) and the surface of its branched hole is strong, strong physical absorption between liquid here and trunk hole (2) surface Instigate the flowing of liquid in trunk hole (2) become liquid of critical trunk hole (2) diameter of continuous media flowing not less than 30nm with Trunk hole (2) is instigated in weak physical absorption between physical absorption between trunk hole (2) surface, liquid here and trunk hole (2) surface Middle liquid flowing becomes liquid of critical trunk hole (2) diameter of continuous media flowing no more than 10nm and trunk hole (2) surface Between physical absorption;Branched hole (3) diameter is in nanometer scale, branched hole (3) radius RB, 1It is taken as (0.1~0.2) Rcr, here RcrInstitute is flowed to make that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) become continuous media The critical cylindrical hole radius needed;Each branch's hole length l1It is as small as possible to reduce the flow resistance of filter opening, l1Value it is strong according to filter opening Degree requires determination, the radius R of trunk hole (2)B, 2Than its branch pore radius RB, 1Bigger, trunk hole (2) and its six branches The through-hole for the tree that hole is formed runs through solid material (1) in the thickness direction of solid material (1), and trunk hole (2) are for subtracting It is small by isolation of purified liquid the inner flow resistance of solid material (1), increase solid material (1) penetrating power, this layer of solid Material (1) is filter membrane.
2. the novel tree-shaped nanoscale cylinder that a kind of branch's hole count for Liquid-liquid separation as described in claim 1 is 6 Hole filter membrane, it is characterised in that:Trunk hole (2) radius RB, 2According to its branch pore radius RB, 1And the object between trunk hole (2) surface Reason adsorbs maximum penetrating power of that liquid in filter membrane in weak liquid mixture and requires to be calculate by the following formula determination:
Here, λ0=ll/ l, l are the thickness of thickness, that is, filter membrane of solid material (1),Req=clRB, l, RcrInstitute is flowed to make that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) become continuous media The critical cylindrical hole radius needed, c1Value range be:1.40~1.72, c1Preferred value be 1.56,ρ is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure Liquid mixture in that liquid body phase density,Physical absorption is weak between the surface of trunk hole (2) That liquid in liquid mixture is R in radiuseqHole radial direction averag density, this averag density withHave It closes,η is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure Liquid mixture in that liquid bulk viscosity,Physical absorption is weak between the surface of trunk hole (2) That liquid in liquid mixture is R in radiuseqHole radial direction equivalent viscosity, this equivalent viscosity withHave It closes,It is R to describe that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) in radiuseq Hole radial direction present Discontinuous transmission effect parameter.
3. the novel tree-shaped nanoscale cylinder that a kind of branch's hole count for Liquid-liquid separation as described in claim 1 is 6 Hole filter membrane, it is characterised in that:Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branched hole (8) it is evenly distributed on a circumference on the surface of solid material (1), the radius of the circumference is Rd, contiguous branch hole is in the circle Spacing on week is Δ1, Δ1With RB, 1Ratio value range be:ks1/RB, 1=0.05~0.5, RdWith RB, 1Ratio For:Rd/RB, 1=(6+3kd)/π。
4. the novel tree-shaped nanoscale cylinder that a kind of branch's hole count for Liquid-liquid separation as described in claim 1 is 6 Hole filter membrane, it is characterised in that:Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branched hole (8) parallelism tolerance of axial line and the axial line in their trunk hole (2) is not more than 0.1l1
5. the novel tree-shaped nanoscale cylinder that a kind of branch's hole count for Liquid-liquid separation as claimed in claim 3 is 6 Hole filter membrane, it is characterised in that:Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7) and branched hole (8) concentricity tolerance in the distribution circle on the surface of solid material (1) and trunk hole (2) is not more than 0.1Rd
6. the novel tree-shaped that a kind of branch's hole count for Liquid-liquid separation as described in any one in claim 1-5 is 6 is received Meter level cylindrical hole filter membrane, it is characterised in that:Filter membrane is plane or curved surface filter membrane.
7. the novel tree-shaped that a kind of branch's hole count for Liquid-liquid separation as described in any one in claim 1-5 is 6 is received Meter level cylindrical hole filter membrane, it is characterised in that:The thickness of filter membrane is identical everywhere or differs.
8. the novel tree-shaped that a kind of branch's hole count for Liquid-liquid separation as described in any one in claim 1-5 is 6 is received Meter level cylindrical hole filter membrane, it is characterised in that:Filter membrane is fabricated by silica or graphene.
CN201810431156.3A 2018-04-27 2018-04-27 The novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count for Liquid-liquid separation is 6 Withdrawn CN108619919A (en)

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CN105016504A (en) * 2015-07-14 2015-11-04 无锡市绿之星环保有限公司 Multi-layer oil-water separator and working method therefor
CN105080361A (en) * 2015-08-20 2015-11-25 张哲夫 Polypropylene hollow fiber ultrafiltration membrane coated with polymer composite coating
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5985146A (en) * 1997-07-23 1999-11-16 Trisep Corporation Sanitary rigid shell spiral wound element
CN201216922Y (en) * 2008-06-12 2009-04-08 刘镇江 Seven-aperture PVC ultra-filtration membrane
CN204261563U (en) * 2014-10-20 2015-04-15 江西成必信生物科技有限公司 The aseptic micro-pore-film filtration device of a kind of veterinary drug injection
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